New Zn(II) Coordination Polymers Constructed from Amino-Alcohols

Article pubs.acs.org/crystal

New Zn(II) Coordination Polymers Constructed from Amino-Alcohols and Aromatic Dicarboxylic Acids: Synthesis, Structure, Photocatalytic Properties, and Solid-State Conversion to ZnO Carmen Paraschiv,*,† Andrei Cucos,† Sergiu Shova,‡ Augustin M. Madalan,§ Catalin Maxim,§ Diana Visinescu,∥ Bogdan Cojocaru,⊥ Vasile I. Parvulescu,*,⊥ and Marius Andruh*,§ †

National Institute for Research and Development in Electrical Engineering, ICPE-CA, Splaiul Unirii 313, 030138 Bucharest, Romania “Petru Poni” Institute of Macromolecular Chemistry , Romanian Academy, Aleea Grigore Ghica Voda 41-A, RO-700487 Iasi, Romania § Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Strada Dumbrava Rosie 23, 020464 Bucharest, Romania ∥ Coordination and Supramolecular Chemistry Laboratory, “Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, Splaiul Independentei 202, 060021 Bucharest, Romania ⊥ Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest, Romania ‡

S Supporting Information *

ABSTRACT: Four new coordination polymers have been obtained solvothermally from the reactions of Zn(NO3)2·6H2O with 1,2-, 1,3-, or 1,4-benzedicarboxylic acids in the presence of ∞ various amino-alcohols: ∞ 1 [Zn2(Htea)2(1,2-bdc)] (1), 1 [Zn(H3tris)(1,3-bdc)(CH3OH)] (2), ∞ ∞ 3 [Zn5(Htea)2(1,3-bdc)3(H2O)]·2.6H2O (3), and 3 [Zn3(H2dea)2(1,4-bdc)3] (4) (H3tea = triethanolamine, H3tris = tris(hydroxymethyl)aminomethane, H2dea = diethanolamine, 1,2H2bdc =1,2-benzenedicarboxylic acid, 1,3-H2bdc =1,3-benzenedicarboxylic acid, and 1,4-H2bdc =1,4benzenedicarboxylic acid). Their crystal structures, thermogravimetric analyses, solid-state transformation to ZnO and characterization of the resultant zinc oxide particles are reported. Compounds 1 and 2 show three-dimensional (3D) supramolecular architectures, generated from the interconnection of the zigzag (in 1) and respectively the linear (in 2) chains through hydrogen bonding interactions. The crystal structure of 3 revealed the presence of five different types of zinc atoms that are successively linked through carboxilato or alkoxo bridges in a helicoidal chain running along the crystallographic a axis. Both right-handed (P) and left-handed (M) helices are present in the crystal, and they are alternately interconnected by pairs of isophthalato bridges, resulting in channels of hexagonal shape, filled with water molecules. Compound 4 has a 3D structure in which linear centrosymmetric {Zn3(H2dea)2}6+ nodes are joined by terephthalate bridges. Owing to its porous network, compound 3 was tested in two selective reactions: photooxidation of phenol to hydroquinone and aerobic photooxidative condensation of benzylamine to N-benzylidenebenzylamine.

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INTRODUCTION The chemistry of multifunctional coordination polymers (CPs) has rapidly become one of the most challenging and appealing research areas due to their potential in both traditional and emerging applications: gas storage,1−8 separation,9−15 catalysis,16−23 luminescence,24−30 recognition,31−33 bioactive molecules,34−37 and magnetism.38−45 A rich variety of structures and topologies have been rationally designed and synthesized by judicious selection of connectors (metal ions or metal clusters) and linkers (organic molecules, inorganic anions, or metalloligands).46−50 The sum of the distinctive characteristics of the inorganic and organic components and their possible synergistic action could provide novel and intriguing properties for the resulting materials. Furthermore, the final architecture can be influenced by auxiliary ligands, solvent molecules, temperature, pH, and coordinated or uncoordinated anions. Numerous multitopic ligands with two or more discrete metal-binding sites have been used in the construction of © 2014 American Chemical Society

coordination polymers. Conventional linkers are usually organic compounds containing donor atoms or groups of donor atoms (polycarboxylates,51−59 phenolates,60−62 amines,63−67 pyridyl derivatives,68−80 sulfonates,81−87 phosphonates,88,89 and azolates90−93). In particular, carboxylate-based systems, especially three-dimensional (3D) porous metal organic frameworks (MOFs) constructed with rigid aromatic backbones (benzene-, naphthalene-, anthracene-, and pyrene-based derivatives), have attracted considerable attention due to the tunability of their structures and properties and their suitability for hydrogen storage, sorption, separation, and sensing.94−102 The node-and-spacer approach103,104 proved to be a successful strategy for the synthesis of coordination polymers. In a series of works, we developed an extension of the classical Received: October 31, 2014 Revised: December 13, 2014 Published: December 19, 2014 799

DOI: 10.1021/cg501604c Cryst. Growth Des. 2015, 15, 799−811

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Crystal Growth & Design

in large quantities at a low cost for the synthesis of CPs, this strategy for obtaining ZnO materials is relatively cheap and accessible. In this work, we report the synthesis of four CPs: ∞ ∞ 1 [Zn 2 (Htea) 2 (1,2-bdc)] (1), 1 [Zn(H 3 tris)(1,3-bdc)∞ (CH3OH)] (2), 3 [Zn5(Htea)2(1,3-bdc)3(H2O)]·2.6H2O (3), ∞ 3 [Zn3(H2dea)2(1,4-bdc)3] (4) (H3tea = triethanolamine, H3tris = tris(hydroxymethyl)aminomethane, H2dea = diethanolamine, 1,2-H2bdc =1,2-benzenedicarboxylic acid, 1,3-H2bdc =1,3benzenedicarboxylic acid, 1,4-H2bdc =1,4-benzenedicarboxylic acid). The three dicarboxylic acids were employed to explore and establish the effect of the position of carboxyl groups on the network topologies in the isolated products. The crystal structures of the four compounds, thermogravimetric analyses, solid-state transformation to ZnO, and characterization of the resultant zinc oxide particles are reported. The porous network of compound 3 prompted us to test it in two selective reactions: photooxidation of phenol to hydroquinone and aerobic photooxidative condensation of benzylamine to N-benzylidenebenzylamine.

approach, showing that alkoxo-bridged Cu(II) cationic species can be used as nodes in constructing extended structures by connecting them through a large variety of spacers (neutral or anionic).105−112 As a follow-up to this research, we decided to employ the Zn(II) ion for the construction of coordination polymers based on amino-alcohols and different multitopic ligands. The spherical d10 configuration is correlated with a flexible coordination environment, and various geometries of Zn(II) complexes are possible: from tetrahedral through trigonal bipyramidal and square pyramidal to octahedral, with more or less severe distortions of these ideal polyhedra. Alkoxobridged Zn(II) systems are scarce,113−117 and coordination polymers consisting of alkoxo-bridged Zn(II) cores and anionic polycarboxylate spacers have not been reported until recently.118−120 A series of zinc(II)−trimesate MOFs obtained under solvothermal conditions in the presence of various amino-alcohols has been described,118 while the reaction of zinc nitrate, terephthalic acid, and triethanolamine afforded another MOF with formula [Zn4(H2tea)2(1,4-bdc)3]·2(MeOH).119 Another study presents several discrete zinc(II)−triethanolamine−acetate complexes, which were further used as precursors for ZnO nanoparticles.120 Many polymeric zinc complexes are characterized by robust and thermally stable open-framework structures and some of them were already evaluated as heterogeneous photocatalysts, due to their versatility in a wide range of reactions.121−123 Selective oxidation using recoverable heterogeneous catalysts has become an important target of the most recent decades, representing the most important strategy to selectively introduce oxygen atoms in organic molecules.124 The development of new types of heterogeneous catalytic systems for liquid-phase oxidations represents an excellent example of green chemistry where environmentally friendly oxidants (hydrogen peroxide and air) lead to an unprecedented increase of the e-factor.125 N-Benzylidenebenzylamine and hydroquinone are important intermediate molecules that are expected to be manufactured via this strategy. Particularly, the selective aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine is an important reaction in organic chemistry since the product of reaction is a valuable intermediate in organic synthesis with direct applications in the production of fine chemicals, pharmaceutics, and agrochemicals, etc.126−128 To replace the stoichiometric oxidants,129,130 heterogeneous metal catalysts (Ru, Rh, Pt, Ir, Pd, Ag, Au) deposited on supports at relatively high temperatures have been used.131−133 More recently, an iron(III)−1,3,5benzenetricarboxylate MOF containing N-hydroxyphthalimide as a guest in the intracrystalline space was reported as a heterogeneous catalyst for the aerobic oxidation of benzylamine and its derivatives to their corresponding benzylimines.134 In the case of dihydroxybenzenes, several M3(BTC)2 metal−organic frameworks (M = Cu(II), Co(II), Ni(II); BTC = 1,3,5benzenetricarboxylate) or Fe-MOF-74 were employed as catalysts.135,136 Another recent application of CPs is their use in the preparation of oxide materials. The potential of Zn(II) molecular compounds as precursors for ZnO phases has been investigated, and it has been shown that particles with controlled morphologies could be generated. Thermal decomposition represents a suitable way to tailor the properties of the ZnObased materials, and both the starting compound and the thermal treatment play a key role in the features and properties of the obtained materials.137−139 By employing ligands available

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EXPERIMENTAL SECTION

Materials. All chemicals were of reagent grade quality and were used as received from commercial sources without further purification. Physical Measurements. FTIR spectra were recorded on KBr pellets in the 400−4000 cm−1 range using a Bruker TENSOR 27 FTIR spectrometer. Elemental analyses (C, H, N) were performed on a EuroVector EA3000 CHNS-O elemental analyzer. HPLC measurements were performed on Agilent Technologies 1260 Infinity with diode array detector (DAD; column Eurosphere C18; flow rate of 1 mL/min; CAN: H2O = 40:60, λ = 274.5 nm, Vinj = 10 μL). The total organic carbon (TOC) analysis was carried out with a HiPerTOC Thermo Electron analyzer that allows the measurement of both total carbon and total inorganic carbon. GC measurements were performed on a K072320 Thermo Quest chromatograph equipped with a FID and a capillary column of 30 m length with DB5 stationary phase. Raman spectra were recorded with a Horiba JobinYvon−Labram HR UV−visible−near-IR Raman microscope spectrometer. PXRD patterns were recorded on a Bruker D8 ADVANCE diffractometer. SEM measurements were carried out on a Carl Zeiss SMT FESEM-FIB Workstation Auriga. The TG/DTG/DTA+FTIR measurements were performed on a Netzsch STA 409 PC thermal analyzer coupled to a Bruker Tensor 27 FTIR spectrometer equipped with a TG-IR gas cell. Samples weighing approximately 20 mg were placed in a cylindrical Al2O3 holder and heated in synthetic air flow (100 mL min−1, purity 99.999%), from room temperature to 600 °C, at a heating rate of 10 °C min−1. An empty Al2O3 holder was used as reference. The FTIR spectra were collected continuously during measurements in the wavenumber range of 650−4000 cm−1 at a resolution of 4 cm−1. X-ray Crystallography. Single-crystal X-ray diffraction measurements were performed on STOE IPDS II diffractometer operating with a Mo Kα (λ = 0.71073 Å) X-ray tube with a graphite monochromator for complexes 2 and 4 and on an Xcalibur Eos 455 diffractometer operating with Mo Kα (λ = 0.71073 Å) X-ray tube with 456 graphite monochromator for complexes 1 and 3. The structures were solved by direct methods and refined by full-matrix least-squares techniques based on F2. The non-H atoms were refined with anisotropic displacement parameters. Calculations were performed using the SHELX-97140 crystallographic software package. A summary of the crystallographic data and the structure refinement for 1−4 is given in Table 1. CCDC reference numbers: 1031382−1031385. Syntheses. ∞1[Zn2(Htea)(1,2-bdc)] (1). A mixture of Zn(NO3)2· 6H2O (0.3 g, 1 mmol), H3tea (0.6 g, 4 mmol), 1,2-benzenedicarboxylic acid (0.17 g, 1 mmol), and Et3N (0.2 g, 2 mmol) in methanol (20 mL) was sealed in a Teflon-lined stainless steel container, heated at 110 °C for 20 h, and then slowly cooled to room temperature. The resultant colorless crystals were washed with methanol and dried in air. Yield: 800


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Table 1. Crystallographic Data, Details of Data Collection, and Structure Refinement Parameters for Compounds 1 - 4 compound

1

2

3

4

chem formula M (g mol−1) temp (K) wavelength (Å) cryst syst space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dc (g cm−3) μ (mm−1) F(000) goodness-of-fit on F2 final R1, wR2 [I > 2σ(I)] R1, wR2 (all data) largest diff peak and hole (e Å−3)

C14H16NO7Zn2 441.02 173.05(10) 0.71073 monoclinic P21/c 9.3186(3) 13.9878(4) 12.2722(3) 90 102.371(3) 90 1562.51(8) 4 1.875 3.107 892 1.051 0.0351, 0.0457 0.742, 0.789 0.971, −0.710

C13H19NO8Zn 382.66 293(2) 0.71073 monoclinic P21/n 10.2338(7) 8.3870(4) 18.4587(14) 90 94.877(6) 90 1578.59(18) 4 1.610 1.597 792 1.202 0.0436, 0.1210 0.0542, 0.1259 0.385, −0.344

C36H45.20N2O21.60Zn5 1178.39 173.05(10) 0.71073 triclinic P1̅ 13.6546(18) 14.2126(18) 14.6377(19) 76.057(11) 86.390(11) 67.910(12) 2553.4(6) 2 1.533 2.388 1196 0.937 0.0617, 0.1083 0.1299, 0.1445 0.804, −0.968

C32H34N2O16Zn3 898.72 173 0.71073 monoclinic P21/n 9.9286(5) 16.0382(10) 10.6658(5) 90 101.588(4) 90 1663.77(15) 2 1.794 2.227 916 1.021 0.0480, 0.1014 0.1081, 0.1419 1.231, −1.397

365 nm (2 × 120 W Vilber Lourmat VL-340.BL, 11520 Lm, 33672 lx), and under visible light with a visible lamp (150 W Philips Master Color CDM-T 150W/830, 13500 Lm, 5810 lx). Control experiments were carried out testing substrates irradiated without catalysts and with catalysts stirred in the darkness. In all of these cases the conversion of substrates was zero. The reaction efficiency (conversion) was calculated from the area of peaks from the chromatograms (which is proportional with the moles of transformed phenol or amine):

45%. Elem. Anal.: 38.12% C, 3.66% H, 3.18% N (calcd);. 37.9% C, 3.64% H, 3.19% N (found). IR (cm−1, KBr): 3252 w, 2960 m, 2910 w, 2853 m, 1604 s, 1582 vs, 1561 vs, 1486 m, 1446 m, 1406 vs, 1382 s, 1271 w, 1087 m, 1069 m, 1023 m, 896 m, 775 m, 695 m, 656 w, 622 w, 510 w, 485 w. ∞ 1 [Zn(H3tris)(1,3-bdc)(CH3OH)] (2). Compound 2 was synthesized with a procedure similar to that used for 1 except that equal moles of H3tris were used in place of H3tea. Yield: 5%. Elem. Anal.: 40.8% C, 5% H, 3.66% N (calcd); 40.8% C, 4.85% H, 3.69% N (found). IR (cm−1, KBr): 3457 br, 3310 m, 3249 s, 2943 w, 1622 s, 1622 s, 1601 m, 1578 s, 1550 m, 1435 s, 1405 m, 1373 s, 1078 m, 1051 m, 1026 m, 751 m, 717 s, 636 w. ∞ 3 [Zn5(Htea)2(1,3-bdc)3(H2O)]·2.6H2O (3). A mixture of Zn(NO3)2· 6H2O (0.3 g, 1 mmol), H3tea (0.3 g, 2 mmol), 1,3-benzenedicarboxylic acid (0.17 g, 1 mmol), and Et3N (0.2 g, 2 mmol) in methanol (20 mL) was sealed in a Teflon-lined stainless steel container, heated at 110 °C for 20 h, and then slowly cooled to room temperature. The resultant colorless crystals were washed with methanol and dried in air. Yield: 34%. Elem. Anal.: 36.75% C, 3.7% H, 2.38% N (calcd); 37% C, 3.64% H, 2.39% N (found). IR (cm−1, KBr): 3070 w, 2963 w, 2897 w, 2854 w, 1608 s, 1558 s, 1448 m, 1395 s, 1276 w, 1064 m, 891 m, 743 s, 714 m. ∞ 3 [Zn3(H2dea)2(1,4-bdc)3] (4). A mixture of Zn(NO3)2·6H2O (0.3 g, 1 mmol), H2dea (0.21 g, 2 mmol), 1,4-benzenedicarboxylic acid (0.17 g, 1 mmol), and Et3N (0.2 g, 2 mmol) in methanol (15 mL) was sealed in a Teflon-lined stainless steel container, heated at 110 °C for 20 h, and then slowly cooled to room temperature. The resultant colorless crystals were washed with methanol and dried in air. Yield: 57%. Elem. Anal.: 42.76% C, 3.81% H, 3.12% N (calcd); 42.1% C, 3.89% H, 3.15% N (found). IR (cm−1, KBr): 3497 w, 3272 w, 1602 s, 1504 m, 1371 s, 1069 m, 1053 m, 1017 w, 847 w, 826 m, 812 m, 750 s, 534 m. Catalytic Tests. Selective Photooxidation of Phenol. In a typical phenol oxidation experiment, 15 mg of photocatalyst 3 were added to a 10 mL aqueous solution of 40 ppm phenol. Samples were irradiated for 3 h, and 30 μL of solution was collected at 30 min intervals for high performance liquid chromatography. Photooxidative Condensation of Benzylamine to N-Benzylidenebenzylamine. The benzylamine selective photooxidation experiments were solvent free. This matches one of the requirements of green chemistry. In a typical experiment 50 mg of 3 was added to 2 mL of benzylamine. Samples were irradiated for 2 h with 30 μL collected after each hour for gas chromatography analysis. Both sets of reactions were carried out by irradiation in the following conditions: under UV light with a UV lamp centered at

C=

Ai − Af × 100 Ai

(1)

where: Ai = area of the peak of the substrate subject of the reaction and Af = area of the peak of the substrate in the reaction mixture. TOF values were calculated on this basis. The selectivity to the product of interest was calculated from the area of the peaks of the products:

S=

A pi ∑ Ap

× 100 (2)

where: Api = area of the peak of the product of interest and ΣAp = sum of area of all the products. Stability of the Photocatalyst 3. The stability of the catalyst paralleled with the evolution of the reaction was checked by ex situ experiments using Raman spectroscopy. Raman calibration was achieved using the Si 520.7 cm−1 peak. The reaction suspension was analyzed every 15 min at 514 nm in the extended spectral region from 300 up to 1500 cm−1. The suspension was taken from the test tube and poured in a liquid Macro-CH-Vis cell accessory. The analysis of the solid was carried out in the 150−4000 cm−1 spectral region using a 633 nm laser. Before analysis, the solid was removed from the reaction mixture and dried.

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RESULTS AND DISCUSSION Crystal Structure Description.∞1[Zn2(Htea)(1,2-bdc)] (1). Solvothermal treatment of phthalic acid with zinc(II) nitrate in the presence of triethanolamine led to a one-dimensional coordination polymer (Figure 1a). Compound 1 crystallizes in the P121/c monoclinic space group, with cell parameters and structure refinement details given in Table 1. The asymmetric 801


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Figure 1. (a) Fragment of the zigzag chain in 1 with atom numbering scheme (symmetry code: ′ = x, 1.5 − y, −0.5 + z); (b) packing diagram showing the interchain hydrogen bonding interactions.

is hexacoordinated with a strongly distorted octahedral geometry: one nitrogen and one oxygen atom from a H3tris molecule [Zn1−N1 = 2.070(4); Zn1−O7 = 2.206(4) Å], three carboxylato oxygens [Zn1−O1 = 2.015(3); Zn1−O3 = 2.449(3); Zn1−O4 = 2.046(3) Å], and a coordinated methanol molecule [Zn1−O1M = 2.085(4) Å]. The Zn···Zn distance within the resultant linear chain is 10.23 Å. This is very close to that found (10.13 Å) within a linear {Zn(1,3-bdc)}n chain in the complex [Zn(μ-3,3′bpp)(1,3-bdc)]n·nCH3OH·2nH2O (3,3′-bpp = 2,2′-bis(3-pyridylmethyleneoxy)-1,1′-biphenylene).141 The linear chains run along the crystallographic a axis, and they are interconnected through hydrogen bonds involving the uncoordinated OH groups from the H3tris molecules and two carboxylato oxygen atoms from an adjacent chain [O6−O1′ = 2.640 Å; O5−O4′ = 2.857 Å (′ = x, 1 + y, z)], resulting in layers parallel to the crystallographic ab plane (Figure 2c). These layers are further interconnected into a complex noncovalent 3D network through strong hydrogen bonds established between the uncoordinated OH groups of the H3tris ligand with the coordinated ones and also with the oxygen atoms from the methanol ligands [O6−O7‴ = 2.630 Å; O5−O1M″ = 2.673 Å (″ = 1 − x, 1 − y, 1 − z; ‴ = 0.5 − x, 0.5 + y, 0.5 − z)] (Figure 2b). ∞ 3 [Zn5(Htea)2(1,3-bdc)3(H2O)]·2.6H2O (3). Compound 3 crystallizes in the P1̅ triclinic space group, with cell parameters and structure refinement details given in Table 1. The asymmetric unit consists of five crystallographically independent Zn(II) ions, two Htea2− anions, three 1,3-bdc2− anions, and 3.6 water molecules (Figure 3). The investigation of the crystal structure reveals the formation of a zigzag chain, which can be viewed as being constructed by alternating {Zn3} and {Zn2} secondary building units (SBUs), involving Zn1, Zn2, and Zn3 atoms and Zn4 and Zn5 atoms, respectively. In the trinuclear

units consist of two crystallographically independent Zn(II) ions, one doubly deprotonated triethanolamine molecule (Htea2−) and one 1,2-bdc2− anion. The two carboxylato groups belonging to the phthalate ligand exhibit different coordination modes: one acts as a syn−syn bridge (μ2−η1:η1), while the second one coordinates in the monodentate mode (μ1−η1:η0). The Zn1 atom is five-coordinated, showing a slightly distorted trigonal bipyramidal geometry (the value of the distortion parameter τ141 is 0.92). The equatorial plane is occupied by the three oxygen atoms from the Htea2− ligand [Zn1−O5 = 1.979(2) Å; Zn1−O6 =1.981(2); Zn1−O7 = 2.131(2)], while the amino nitrogen [Zn1−N1 = 2.146(3) Å] and one carboxylato oxygen [Zn1−O1 = 1.975(2) Å] fill the axial positions. The Zn2 atom displays a tetrahedral stereochemistry, with two alkoxo oxygen atoms from two triethanolamine molecules and two carboxylato oxygens, one from the syn−syn bridge and one from a monodentate group. The Zn2−O distances are in the 1.923(2)−2.007(2) Å range. The zinc atoms are connected through one syn−syn carboxylato and two alkoxo bridges, resulting in zigzag chains running along the crystallographic c axis. The Zn···Zn separations are 3.414 and 3.535 Å. The chains are further interconnected (Figure 1b) through hydrogen bonds established between the protonated OH groups from the Htea2− molecules and the uncoordinated oxygen atoms of the phthalate ligands (O7′···O3 = 2.7 Å, ′ = 1 − x, 1 − y, 1 − z). ∞ 1 [Zn(H3tris)(1,3-bdc)(CH3OH)] (2). The self-assembly process involving zinc(II) ion, H3tris, and isophthalate anion led to the formation of a one-dimensional coordination polymer, in which the bridging isophthalato ligands connect [Zn(H3tris)(CH3OH)]2+ nodes (Figure 2a). The two carboxylato groups belonging to the isophthalate anion exhibit different coordination modes: bidentate chelating and monodentate. The zinc ion 802


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Figure 2. (a) Coordination environment of the zinc ion in 2 with the atom labeling scheme [′ = −1 + x, y, z]; (b and c) packing diagrams showing the hydrogen bonding interactions leading to the 3D and 2D, respectively, supramolecular networks.

{Zn3} SBU the two terminal zinc atoms, Zn1 and Zn3, show a coordination number of 5, but their coordination geometries are different. Both triethanolamine molecules are doubly deprotonated and coordinate as tetradentate ligands to Zn1 and Zn3. The Zn1 ion displays a distorted square pyramidal geometry, with the trigonal distortion parameter τ = 0.43. The basal plane is defined by two alkoxo oxygen atoms, one amino nitrogen, and one oxygen atom from one 1,3-bdc ligand [Zn1− O16 = 2.018(5); Zn1−O17 =1.991(5); Zn1−N2 = 2.155(6); Zn1−O15 = 1.969(5) Å], while the fifth coordination site is occupied by the protonated oxygen atom from the Htea2− molecule [Zn1−O18 = 2.089(5) Å]. The value of the τ parameter for Zn3 ion is 0.87, indicating a slightly distorted trigonal bipyramidal geometry. The equatorial plane is occupied by the three oxygen atoms from the triethanolamine molecule [Zn3−O7 = 2.031(5); Zn3−O8 = 2.062(5); Zn3−O9 = 1.990(5) Å], while the amino nitrogen and one oxygen atom from a carboxylato bridge fill the axial positions in a nearly linear arrangement [O10−Zn3−N1 = 173.4°]. The coordination environment of the central atom of the trinuclear SBU, Zn2, is a slightly distorted octahedron and consists of six oxygen atoms: three from three isophthalate ligands [Zn2−O11 = 2.079(5); Zn2−O13 = 2.075(5); Zn2− O14 = 2.121(5) Å], two alkoxo bridges [Zn2−O9 = 2.148(5);

Figure 3. Asymmetric unit in 3 with the atom labeling scheme [′ = 1 + x, y, z].

Zn3−O16 = 2.084(5) Å], and one terminal aqua ligand [Zn2− O1W = 2.166(5) Å]. 803


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Figure 4. (a) Fragment of the helicoidal chain in 3 running along the crystallographic a axis; (b) helices of opposite chirality interconnected by pairs of isophthalato bridges (the Htea2− molecules and the carbon atoms of the aromatic rings have been omitted for clarity).

Figure 5. (a) Packing diagram of 3 showing hexagonal channels formed along the crystallographic a axis; (b) alternating P- and M-helices within the channels (the lattice water, the Htea2− ligands, and the carbon atoms of the aromatic rings have been omitted for clarity).

between three zinc atoms, similarly to that as reported with the tetranuclear Zn4(Htea)2Ac4 cluster.120 The Zn···Zn separations within the chains vary from 3.258 to 3.397 Å. Both right-handed (P) and left-handed (M) helices are present in the crystal, and they are alternately interconnected by pairs of isophthalato bridges (Figure 4b), resulting in a 3D porous network. There are three crystallographically different types of isophthalate anions: two of them have all of the four O atoms coordinated to four zinc ions (μ4−η1:η1:η1:η1 mode), while the third one presents a μ4−η1:η1:η2 coordination mode. An inspection of the packing diagram along the crystallographic

The binuclear {Zn2} unit is a [Zn2(COO)3] SBU that was also found within other compounds.118,142−145 Both Zn4 and Zn5 atoms show a tetrahedral stereochemistry, with four oxygen atoms arising from one alkoxo and three isophthalato bridges. The Zn4−O distances vary between 1.927(5) and 1.948(5) Å, while the Zn5−O bonds are in the 1.905(4)− 1.992(5) Å range. The binuclear and trinuclear secondary building units are alternately connected by alkoxo bridges into helicoidal chains running along the crystallographic a axis, with a helical pitch of 13.66 Å (Figure 4a). Each Htea2− ligand acts as a bridge 804


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Crystal Growth & Design a axis reveals channels of hexagonal shape (Figure 5). The edges of the hexagon are equal to 8.36, 8.57, and 9.47 Å, respectively. The shorter edges correspond to μ4−η1:η1:η1:η1 isophthalato bridges, while the longest ones arise from the μ4−η1:η1:η2 bridges. The cavities are filled with water molecules and have diameters of 7.4 Å, as found by PLATON (taking into account the van der Waals radii of the atoms).146 The solvent-accessible volume of 3 calculated by PLATON (excluding all water molecules from the pores) is 747.4 Å3, corresponding to 29.3% of the unit cell volume. ∞ 3 [Zn3(H2dea)2(1,4-bdc)3] (4). The terephthalate anion is a rigid dicarboxylate linker, which has been extensively used to generate extended structures. The self-assembly process between Zn(II) ion, diethanolamine, and deprotonated terephthalic acid affords a 3D network built from centrosymmetric {Zn3(H2dea)2}6+ nodes and terephthalato bridges. The synergistic use of diethanolamine and 1,4-bdc 2− linker generates a linear Zn3(COO)6 secondary building unit, which was also reported for several Zn(II) systems with various carboxylate ligands.147−161 Compound 4 crystallizes in the monoclinic P21/n space group. The central Zn1 atom is surrounded by six carboxylato oxygen atoms in a nearly perfect octahedral geometry, with Zn−O bond lengths between 2.058(3) and 2.174(5) Å and O−Zn−O bond angles between 89.89(9)° and 93.62(9)° (Figure 6). Selected bond distances and angles for compound 4 are collected in Table 2. The diethanolamine molecule is not

deprotonated and coordinates as a bidentate chelating ligand toward Zn2 ions through the nitrogen atom and one oxygen, while the other OH group remains uncoordinated. The coordination sphere of the Zn2 ion is defined by one nitrogen and one oxygen atom from a diethanolamine molecule and four oxygen atoms from three terephthalate anions. Two of the carboxylato groups act as bridges in the μ2−η1:η1 syn−syn mode, while the third one coordinates in a bridging-chelating μ2−η1:η2 fashion. The geometry of Zn2 atoms is a distorted octahedron, with Zn2−O/N bond lengths between 2.008(2) and 2.328(3) Å and bond angles between 76.94(11)° and 103.04(9)°. The distance between the zinc centers within the node is 3.462 Å. The terephthalate anions connect the {Zn3(H2dea)2}6+ nodes into a 3D network, in which narrow channels of triangular shape are formed (Figure 7). There are no solvent molecules within the cavities. Photocatalytic Studies. Compound 3 was tested as catalyst in two reactions, namely, the photooxidations of phenol and benzylamine. Photooxidation of Phenol to Hydroquinone. The evolution of phenol photooxidation is presented in Figure 8. A conversion of about 20% was achieved after 180 min disregarding the irradiation source (UV or vis). These results (determined on the basis of the HPLC analysis) are in a perfect concordance with the TOC measurements of the reaction product. No mineralization or loss of carbon has been identified. The only identified product was hydroquinone. However, it is important to underline that the investigated photocatalyst 3 led very similar results under both vis and UV irradiation conditions. Moreover, under vis irradiation, the activity was slightly higher for short reaction times. Photooxidative Condensation of Benzylamine to NBenzylidenebenzylamine. A possible mechanism for the selective photooxidation of benzylamine to N-benzylidenebenzylamine is presented in Scheme 1. The photocatalytic activity of 3 can be associated with absorption of light radiation by the chromophore building blocks, leading to excited sites. Compound 3 acts as an electron donor for molecular oxygen, which gives rise to active oxygen species (superoxide ion) and a positively charged compound (3*+). Benzylamine is further activated by the electron hole of 3 and reacts with the active oxygen species to form benzaldehyde and ammonia. Subsequently, the condensation reaction of benzaldehyde with another benzylamine molecule leads to N-benzylidenebenzylamine. According to previous studies, this second reaction step

Figure 6. Trinuclear unit in 4 together with the atom numbering scheme in the asymmetric unit.

Scheme 1. Oxidative Condensation of Benzylamine Catalyzed by Compound 3

805


a

806

169.51(10) 120.72(9) 113.99(10) 120.55(10) 101.69(9) 101.99(10) 101.99(10) 131.15(10) 106.33(10) 104.37(10) 127.77(12) 121.98(11)

O1−Zn1−N1 O5−Zn1−O6 O5−Zn1−O7 O6−Zn1−O7 O2−Zn2−O6 O2−Zn2−O4′ O2−Zn2−O5′ O6−Zn2−O4′ O6−Zn2−O5′ O4′−Zn2−O5′ Zn2−O5−Zn1 Zn2″−O6−Zn1

O1−Zn1−N1 O1−Zn1−O1M O1−Zn1−O3 O1−Zn1−O4 O1M−Zn1−O7 O3−Zn1−N1 O4−Zn1−N1 N1−Zn1−O7

Zn1−N1 Zn1−O1 Zn1−O3 Zn1−O4 Zn1−O7 Zn1−O1M

compd 2

110.73(14) 94.22(16) 158.95(12) 101.25(13) 174.70(16) 89.41(13) 145.35(14) 78.28(14)

2.070(4) 2.015(3) 2.449(3) 2.046(3) 2.206(4) 2.085(4)

O15−Zn1−N2 O17−Zn1−O16 O16−Zn1−O18 O17−Zn1−O18 O18−Zn1−N2 O11−Zn2−O13 O14−Zn2−O1W O16−Zn2−O9 O10−Zn3−N1 O7−Zn3−O8 O9−Zn3−O7 O9−Zn3−O8 O4−Zn4−O2 O4−Zn4−O6

Zn1−N2 Zn1−O15 Zn1−O16 Zn1−O17 Zn1−O18 Zn2−O11 Zn2−O13 Zn2−O14 Zn2−O16 Zn2−O1W Zn2−O9 Zn3−N1

′ = x, 1.5 − y, −0.5 + z; ″ = x, 1.5 − y, 0.5 + z. b′ = 1 + x, y, z. c′ = −0.5 − x, −0.5 + y, 0.5 − z.

1.975(2) 1.979(2) 1.981(2) 2.131(2) 2.146(3) 2.007(2) 1.932(2) 1.958(2) 1.923(2)

Zn1−O1 Zn1−O5 Zn1−O6 Zn1−O7 Zn1−N1 Zn2−O2 Zn2−O4 Zn2−O5 Zn2−O6

compd 1a

Table 2. Selected Bond Distances (Å) and Angles (deg) for Compounds 1−4

174.9(2) 148.7(2) 105.2(2) 101.1(2) 81.5(2) 171.3(2) 176.5(2) 169.01(18) 173.3(2) 118.7(2) 121.2(2) 115.8(2) 116.2(2) 118.5(2)

2.151(7) 1.960(6) 2.009(5) 1.995(5) 2.068(5) 2.078(5) 2.081(5) 2.123(5) 2.085(5) 2.164(5) 2.149(5) 2.157(6)

compd 3b

O6−Zn4−O2 O7−Zn4−O2 O7−Zn4−O4 O7−Zn4−O6 O17−Zn5−O1 O17−Zn5−O3 O17−Zn5−O5 O3−Zn5−O1 O5−Zn5−O1 O5−Zn5−O3 Zn1−O16−Zn2 Zn3−O9−Zn2 Zn4−O7−Zn3 Zn5−O17′−Zn1′

Zn3−O7 Zn3−O8 Zn3−O9 Zn3−O10 Zn4−O2 Zn4−O4 Zn4−O6 Zn4−O7 Zn5−O1 Zn5−O3 Zn5−O5 Zn5−O17′ 104.1(2) 102.4(2) 104.0(2) 110.6(2) 100.0(2) 107.9(2) 121.4(2) 109.4(2) 103.1(2) 113.5(2) 105.5(2) 109.9(2) 118.1(2) 120.8(3)

2.033(5) 2.049(5) 1.991(5) 1.996(5) 1.950(5) 1.934(5) 1.943(5) 1.928(5) 1.990(5) 1.943(5) 1.943(6) 1.905(5) O5−Zn1−O3 O3−Zn1−O8′ O5−Zn1−O8′ O6−Zn2−N1 O6−Zn2−O1 O6−Zn2−O3 O6−Zn2−O4 O7−Zn2−N1 O7−Zn2−O1 O7−Zn2−O3 O7−Zn2−O4 O7−Zn2−O6 Zn2−O3−Zn1

Zn1−O3 Zn1−O5 Zn1−O8′ Zn2−N1 Zn2−O1 Zn2−O3 Zn2−O4 Zn2−O6 Zn2−O7

compd 4c

89.87(9) 90.51(9) 93.63(10) 91.78(11) 100.46(10) 103.05(9) 162.18(9) 160.88(11) 84.05(10) 101.23(9) 89.29(10) 93.74(10) 107.85(10)

2.175(2) 2.058(2) 2.063(2) 2.179(3) 2.101(2) 2.109(2) 2.328(3) 2.033(2) 2.008(2)

Crystal Growth & Design Article


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Figure 7. Two views of the packing diagram in 4 (the carbon atoms of the aromatic rings have been omitted for clarity).

Figure 10. Time evolution of the content of benzaldehyde in the reaction mixture.

Figure 8. Photooxidation of phenol under UV and visible light irradiation.

Figure 9. Time evolution of TOF and selectivity to Nbenzylidenebenzylamine as a function of the irradiation source.

Figure 11. Liquid Raman spectra of benzylamine before and after 3 h of UV exposure.

is not photocatalyzed and may take place even under dark.162 However, the phtoactivated first step reaction seems to be faster than the non-photoactivated second step condensation, as suggested by the catalytic results (Figure 9). The photooxidative condensation was performed under both UV and vis irradiation and differences in TOF (turnover frequency), and selectivities depending on the two photoactivation sources were found (Figure 9). Working under visible irradiation, TON (turnover number) varied in a small range (38 after 0.5 h irradiation versus 40 after 2 h irradiation). However, during this

period of time TOF decreased from 76 to around 20. Under UV irradiation, both TON and TOF values were initially smaller than under vis irradiation, but they increased with time (TON from 10 after 0.5 h to 70 after 2 h irradiation, and TOF from 19 after 0.5 h to 35 after 2 h irradiation). Differences were also in the selectivity to N-benzylidenebenzylamine, but only for long exposure times. In both cases, the selectivity was higher than 99% for exposure times up to 1.5 h, and then it decreased to 97% under UV and 80% under vis, respectively. The byproduct 807


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integrity (Supporting Information Figure S6). Further reuse of the catalyst in a new batch did not change the Raman spectra or catalytic performances. The diffractograms and Raman spectra of compound 3 before and after the photocatalitic reaction confirm its integrity at the end of the process (Supporting Information Figures S7 and S8). Thermal Stability Studies. In order to investigate the thermal stability of the four coordination polymers, TG-FTIR experiments were carried out in air between room temperature and 600 °C. Detailed descriptions along with the TG/DTG/ DTA diagrams together with 2D plots of FTIR spectra of evolved gases from the decomposition of 1−4 are provided in the Supporting Information (Figures S9−S16). The TG analyses revealed a series of weight losses in the 200−515 °C range, attributed to the elimination of benzenedicarboxylate and amino-alcohol molecules. The decompositions are characterized by several peaks in DTG and DTA, respectively. The overall weight loss is consistent with the zinc oxide formation for all compounds. Conversion to ZnO. ZnO-1−ZnO-4 structures have been generated upon calcinations in air of compounds 1−4 at 800 °C for 1 h, and they were studied by PXRD and scanning electron microscopy. The XRD patterns for ZnO-1−ZnO-4 are similar and match with the standard pattern of the typical wurtzite structure of ZnO (hexagonal phase; space group P63mc, with lattice constants a = 3.24982(9) Å, c/a = 1.6021 Å, Z = 2; JCPDS No. 36-1451). Since all have similar features, only the case of ZnO-3 will be discussed. The sharp diffraction peaks (Figure 12) indicate a good crystallinity of the ZnO particles. No other peaks related to any impurity were observed. Investigation of the SEM images of the structures produced by calcinations revealed aggregates of ZnO crystals with various shapes and sizes (Figure 13). In general, the particles have asymmetric hexagonal shapes with rounded edges, and their

Figure 12. XRD pattern for ZnO−3.

of this photooxidation was benzylaldehyde. The increase of benzylaldehyde content in the product mixture (Figure 10), especially under vis irradiation, can be an indication that the first step of the reaction leading to benzylaldehyde occurs faster than the coupling of benzylaldehyde with the second molecule of benzylamine (Scheme 1), which may cause an accumulation of the oxidation product with time. The stability of 3 as a photocatalyst was investigated using Raman spectroscopy. The Raman spectra of benzylamine before and after 3 h UV exposure (Figure 11) show a decrease of the intensity of the band at about 879 cm −1, which is assigned to the C−NH2 stretch.163 The band at about 1004 cm−1 is assigned to the ring breathing and remains unchanged during the reaction. These results support the fact that only the -NH2 group was oxidized, while the aromatic ring remained unaltered. Similar spectra were collected under vis irradiation (Supporting Information Figure S5). Raman spectra of photocatalyst 3 separated from the reaction mixture at different reaction times demonstrate no change (i.e., no damage) of its

Figure 13. SEM images at different magnifications for ZnO-1−ZnO-4. 808


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diameters range from 60 to 750 nm. The small differences in the morphologies of the four samples show the influence of the crystal structure of coordination polymers upon the features of materials produced from their calcinations.

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CONCLUSION The results reported herein illustrate the rich chemistry which can be generated by using rigid dicarboxylate linkers (linear or angular) together with various amino-alcohols. The combination of two types of ligands imposed both short and long Zn···Zn separations and led to the obtaining of coordination polymers with various dimensionalities and solid-state architectures. In the four compounds, the carboxylate groups exhibit various connectivity modes: monodentate, chelating, syn−syn bridge, and bridging chelating. The solid-state transformation of the Zn(II) coordination polymers is a facile and relatively low-cost method for obtaining ZnO particles with tunable morphologies, which may be influenced by the dimensionality and the structural features of the precursors. Compound 3 proved to be active in the selective photooxidation of phenol and, even more remarkably, in the selective photooxidation of benzylamine to form N-benzylidenebenzylamine. These results are promising and highlight the potential application of these kinds of materials in photocatalysis.

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ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic data in CIF format, figures showing calculated and experimental PXRD, Raman spectra, TG/DTG/ DTA curves, and 2D plots of FTIR spectra, and text giving additional information regarding thermal analysis measurements and FTIR analysis of evolved gases. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (C.P.). *E-mail: [email protected] (V.I.P.). *E-mail: [email protected] (M.A.). Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support from the Romanian Ministry of Education CNCS-UEFISCDI (Projects PN-II-RU-TE-2012-3-0390 and PNII-ID-PCCE-2011-2-0050) is gratefully acknowledged.

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